Liu Ying-Jie, Liu Yu, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, Key Laboratory of Special Environmental Functional Materials (Zhengzhou University), Ministry of Education, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, People's Republic of China.
Angew Chem Int Ed Engl. 2023 Nov 6;62(45):e202311572. doi: 10.1002/anie.202311572. Epub 2023 Sep 28.
Constructing chiral supramolecular assembly and exploring the underlying mechanism are of great significance in promoting the development of circularly polarized luminescence (CPL)-active materials. Herein, we report a solvation-mediated self-assembly from single-crystals to helical nanofibers based on the first protic acyclic (methoxy)(amino)carbenes (pAMACs) Au -enantiomers driven by a synergetic aurophilic interactions and H-bonds. Their aggregation-dependent thermally activated delayed fluorescence properties with high quantum yields (Φ ) up to 95 % were proved to be attributed to packing modes of Au⋅⋅⋅Au dimers with π-stacking or one-dimensional extended Au⋅⋅⋅Au chains. Via drop-casting method, supramolecular P- or M-helices were prepared. Detailed studies on the helices demonstrate that formations of extended helical Au⋅⋅⋅Au molecular chains amplify supramolecular chirality, leading to strong CPL with high dissymmetry factor (|g |=0.030, Φ =67 %) and high CPL brightness (B ) of 4.87×10 . Our findings bring new insights into the fabrication of helical structures to improve CPL performance by modifying aurophilic interactions.
构建手性超分子组装体并探索其潜在机制对于促进圆偏振发光（CPL）活性材料的发展具有重要意义。在此，我们报道了一种基于首个质子型非环状（甲氧基）（氨基）卡宾（pAMACs）金对映体，通过协同的金亲金相互作用和氢键驱动，从单晶到螺旋纳米纤维的溶剂化介导自组装。它们具有聚集依赖性热激活延迟荧光性质，量子产率（Φ）高达95%，这被证明归因于具有π堆积的Au⋅⋅⋅Au二聚体或一维延伸的Au⋅⋅⋅Au链的堆积模式。通过滴铸法制备了超分子P-螺旋或M-螺旋。对螺旋的详细研究表明，延伸的螺旋Au⋅⋅⋅Au分子链的形成放大了超分子手性，导致具有高不对称因子（|g| = 0.030，Φ = 67%）和4.87×10的高CPL亮度（B）的强CPL。我们的发现为通过修饰金亲金相互作用来制造螺旋结构以改善CPL性能带来了新的见解。
